US8025826B2 - Glass/polyvinylbutyral laminates having directional surface patterns and a process for preparing same - Google Patents

Glass/polyvinylbutyral laminates having directional surface patterns and a process for preparing same Download PDF

Info

Publication number
US8025826B2
US8025826B2 US12/507,273 US50727309A US8025826B2 US 8025826 B2 US8025826 B2 US 8025826B2 US 50727309 A US50727309 A US 50727309A US 8025826 B2 US8025826 B2 US 8025826B2
Authority
US
United States
Prior art keywords
pattern
polyvinyl butyral
pvb
press
sheet
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related, expires
Application number
US12/507,273
Other versions
US20090277573A1 (en
Inventor
Chul Won Choi
Sang Gyu Lee
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Kuraray America Inc
Original Assignee
EI Du Pont de Nemours and Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Priority claimed from US10/204,128 external-priority patent/US20030012964A1/en
Application filed by EI Du Pont de Nemours and Co filed Critical EI Du Pont de Nemours and Co
Priority to US12/507,273 priority Critical patent/US8025826B2/en
Publication of US20090277573A1 publication Critical patent/US20090277573A1/en
Application granted granted Critical
Publication of US8025826B2 publication Critical patent/US8025826B2/en
Assigned to KURARAY AMERICA INC. reassignment KURARAY AMERICA INC. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: E. I. DU PONT DE NEMOURS AND COMPANY
Adjusted expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Images

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10559—Shape of the cross-section
    • B32B17/10577—Surface roughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B17/00—Layered products essentially comprising sheet glass, or glass, slag, or like fibres
    • B32B17/06—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material
    • B32B17/10—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin
    • B32B17/10005—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing
    • B32B17/1055—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer
    • B32B17/10761—Layered products essentially comprising sheet glass, or glass, slag, or like fibres comprising glass as the main or only constituent of a layer, next to another layer of a specific material of synthetic resin laminated safety glass or glazing characterized by the resin layer, i.e. interlayer containing vinyl acetal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/42—Layered products comprising a layer of synthetic resin comprising condensation resins of aldehydes, e.g. with phenols, ureas or melamines
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/10—Esters; Ether-esters
    • C08K5/101—Esters; Ether-esters of monocarboxylic acids
    • C08K5/103—Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/07—Flat, e.g. panels
    • B29C48/08—Flat, e.g. panels flexible, e.g. films
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/03—3 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/40—Symmetrical or sandwich layers, e.g. ABA, ABCBA, ABCCBA
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/538—Roughness
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/006—Transparent parts other than made from inorganic glass, e.g. polycarbonate glazings
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/24—Structurally defined web or sheet [e.g., overall dimension, etc.]
    • Y10T428/24355—Continuous and nonuniform or irregular surface on layer or component [e.g., roofing, etc.]

Definitions

  • the present invention relates to glass laminates.
  • the present invention particularly relates to laminates of glass and polyvinylbutyral, and a process of preparing same.
  • Glass laminates that include plasticized polyvinyl butyral (PVB) interlayers can be used in various applications, including use in automotive safety glass applications such as windshields and side glass; in architectural applications such as windows, doors and/or building panels; and in various other applications such as in display cases, as shelving, and the like.
  • PVB plasticized polyvinyl butyral
  • Glass/PVB laminates can be prepared by conventional methods. Typically, a laminate can be prepared by first positioning a sheet of PVB between two pieces of glass to obtain an assembly, and trimming the excess PVB interlayer. A “pre-press” is obtained from the assembly by removing air trapped between the glass and the interlayer, and then sealing the edges. A conventional method for edge sealing requires placing the assembly inside of a rubber bag and removing the air from the bag by applying vacuum. The rubber bag and contents can then be passed through a furnace wherein the temperature is increased to about 135° C. in order to obtain the pre-press. A pre-press so obtained can be heated in an autoclave wherein heat and pressure are applied, residual air is dissolved in the PVB interlayer, and bonding occurs between the interlayer and the surface being laminated.
  • An interlayer having a smooth surface can present problems during the assembly and de-airing steps of a lamination process if a vacuum bag system is used to make the pre-press.
  • the smooth pattern allows the interlayer to tack too easily to the glass, making placement of the interlayer difficult.
  • a smooth pattern can lead to a laminate having trapped air, and flaws in the laminate can result therefrom.
  • interlayers having a rough surface can facilitate de-airing.
  • Rough surface patterns can be generated by conventional methods, including use of an embossing tool to impart a reproducible pattern on the surface of the interlayer material. It is also conventional to generate a randomly irregular surface pattern by a melt-fracture process, which can provide channels by which air can escape during the lamination process.
  • the PVB interlayer is first subjected to a shaping step wherein the PVB interlayer is differentially stretched such that the shaped interlayer better conforms to the curvature of the vehicle for which the windshield is designed.
  • the PVB roll is unwound, and the interlayer is heated to approximately 100° C. and then passed over one or more cones which are smooth, and then chilled to approximately 10° C. for storage, and then cut into blanks slightly larger than the size of the windshield. Stresses incurred in the shaping process are partially relaxed as the blanks are conditioned at 10° C.
  • some of the pattern roughness is pressed out temporarily, but will recover according to stress relaxation kinetics well known in the art of polymer rheology.
  • haze in a pre-press can be a problem, especially if the interlayer material is used within twelve hours of being shaped for lamination in a vacuum bag pre-pressing system. Pre-presses with less than 15% light transmission are typically rejected.
  • Use of an embossing tool can be effective in resolving the de-airing and pre-press clarity concerns, but is more costly and more work intensive than use of a melt fracture process.
  • An embossing process is inflexible relative to the melt fracture process, with respect to producing different patterns on the same equipment.
  • the present invention is a plasticized polyvinyl butyral sheet having a directional surface pattern created using a melt fracture process during extrusion of the sheet.
  • the present invention is a plasticized polyvinyl butyral sheet having a washboard surface pattern created using a melt fracture process during extrusion of the sheet.
  • the present invention is a plasticized polyvinyl butyral sheet having a herringbone surface pattern created using a melt fracture process during extrusion of the sheet.
  • the present invention is a process for creating a directional pattern on a surface of a plasticized polyvinyl butyral sheet using a melt fracture process during extrusion of the sheet.
  • the present invention is a laminate comprising a plasticized polyvinyl butyral interlayer, wherein the interlayer is obtained from a polyvinyl butyral sheet having a directional surface pattern created using a melt fracture process during extrusion of the sheet.
  • FIG. 1 is a grey scale image of a portion of the upper surface of a polyvinyl butyral sheet having a herringbone pattern.
  • FIG. 2 is a grey scale image of a portion of the upper surface of a polyvinyl butyral sheet having a washboard pattern.
  • the present invention is a plasticized polyvinyl butyral (PVB) sheet having a roughened surface wherein the surface has directionality imparted by a melt fracture extrusion process.
  • PVB sheeting of the present invention is plasticized.
  • Conventional plasticizers known in the art of preparing PVB sheets can be used in the practice of the present invention. Such plasticizers include, but are not limited to: triethylene glycol-di-2-ethyl butyrate; triethylene glycol-di-2-ethyl hexanoate; and dibutyl sebacate.
  • the roughness of the surface of a PVB sheet of the present invention is such that haze in a glass/PVB pre-press is low even if the PVB is used within 12 hours after it is stretched.
  • Surface roughness can be measured by conventional methods, and can be expressed by the term R z .
  • R z is greater than about 30 micrometers, as determined by ISO R468.
  • a washboard pattern of the present invention has a roughness of greater than about 35, more preferably greater than about 40 and most preferably from about 35 to about 100.
  • the R z is less than about 35, preferably less than about 30, more preferably from about 15 to about 35, and most preferably from about 20 to about 30 micrometers.
  • the rough surface has a directional pattern, and the rough directional pattern is obtained without use of an embossing tool.
  • the present invention is a laminate comprising at least one layer of PVB and at least one layer of glass, wherein the PVB layer is obtained by an extrusion process wherein a roughened PVB surface having directionality is obtained without use of an embossing tool.
  • the laminate is prepared according to conventional methods, wherein an assembly comprising at least one layer of PVB of the present invention is heated, and then de-aired under vacuum and at elevated temperature to form a pre-press.
  • the laminate can be prepared by heating the assembly in an oven and then passing it through one or more pairs of nip rolls.
  • the pre-press can be autoclaved according to conventional methods and conditions to yield a finished laminate article.
  • the present invention is a process for preparing a PVB sheet having a roughened surface having directionality imparted using a melt fracture extrusion process, without the aid of an embossing tool.
  • Directionality refers to the tendency of a roughened pattern of the present invention to have an ordered, repetitive pattern that gives the appearance of an embossed pattern.
  • such a pattern is obtained without using an embossing tool.
  • problems associated with use of an embossing tool are eliminated. Problems associated with use of an embossing tool include, for example, surface defects and material loss caused by adhesion of the sheet material to the tool.
  • a directional surface pattern of the present invention provides ordered channels that are formed by a continuous alignment of the troughs of roughened surface to provide substantially uninterrupted channels for airflow. Uninterrupted channels in a surface pattern can provide the benefit of more efficient “de-airing” in a lamination process than a surface pattern having a random array of peaks and valleys.
  • An extruded sheet of the present invention viewed on a 3-dimensional axis wherein the height and depth of the surface pattern is shown on the y-axis, the sheet length as it is extruded from the extruder is shown on the x-axis, and the depth of the sheet in the cross-web direction is represented on the z-axis, has channels that run in the cross-web direction and that are substantially uninterrupted by the random occurrence of a raised portion of the surface blocking the channel.
  • the present invention provides a process for obtaining a non-random pattern having substantially uninterrupted channels in the cross-web direction without use of an embossing tool.
  • the process comprises varying certain conditions and parameters in the extrusion process of PVB sheeting material.
  • parameters can be varied to control surface pattern.
  • Some parameters that can be varied are die body temperature and die gap, sheet caliper, lip stream pressure, lip gap, air gap, content of plasticizer, temperature of polymer, throughput of molten polymer per unit die width, and temperature of quench water.
  • Other parameters can be varied as well.
  • the directional patterns of the present invention can be obtained in the process of the present invention by varying the die pressure.
  • washboard pattern is one type of directional pattern that can be obtained on the PVB surface.
  • a herringbone pattern is a second type of directional surface pattern that can be obtained in the process of the present invention by varying process conditions.
  • the herringbone and washboard patterns are shown in FIG. 1 and FIG. 2 , respectively.
  • washboard pattern it is meant a regular pattern having substantially uninterrupted channels wherein the troughs, or surface depressions, of an extruded sheet are aligned in the cross-web direction to form substantially straight lines. The lines can run parallel to the front edge of the extruded sheet, or can be at an angle of from about 1° to about 45°.
  • a washboard pattern can be obtained by operating at a die pressure of greater than 58 kg/cm 2 (5.69 MPa).
  • a washboard pattern or surface describes a surface having alternately high ( 1 ) and low ( 2 ) areas of elevation that form ridges ( 3 ), similar to the surface of a washboard.
  • the ridges on a PVB surface of the present invention can be nearly parallel to the cross-web direction of the sheeting as it is extruded, the cross-web direction being the direction perpendicular to that of the extrusion.
  • a herringbone pattern can be obtained on the PVB surface.
  • herringbone pattern it is meant a regular pattern having substantially uninterrupted channels wherein the troughs, or surface depressions, of an extruded sheet are aligned in the cross-web direction to form channels that appear to regularly change direction up and down in an alternating pattern, passing through a mid-line, and creating the appearance of “zig-zag” channels.
  • a herringbone pattern can be obtained by varying die pressure such that the pressure is below 37 kg/cm 2 (3.63 MPa).
  • Other patterns can be obtained by varying process conditions, but the directional patterns of the present invention are controlled primarily by the die pressure.
  • Throughput rate of polymer through the die
  • rate of polymer through the die can be in the range of from about 600 to about 1000 kg per hr per meter, depending on the equipment being used.
  • Example 1-25 100 parts of dry PVB flake of nominally 18-23% by weight of un-butyralated vinyl alcohol groups were mixed with 35-40 parts of tetraethylene glycol di-n-heptanoate plasticizer and one or more light stabilizers marketed under the tradename “Tinuvin” by Ciba-Geigy Co. and an antioxidant which were pre-mixed in the plasticizer continuously in a twin-screw extruder. The melt was forced through a slot die and formed a sheeting of 0.76 mm nominal thickness.
  • agents for modifying surface energy of the bulk interlayer and usual adjuvants such as antioxidants, colorants and ultraviolet absorbers which do not adversely affect the functioning of the surface energy modifying agent and adhesion control agent can be included in the PVB composition.
  • the melt at the die is at approximately 200-220° C.
  • the lips of the die are heated by injecting pressurized steam into cavities therein. The lip temperature is controlled by the pressure of the steam injected.
  • One of the die lips is adjustable so that as it opens, the back-pressure in the die is decreased and vice versa. The position of this lip is computer-controlled, and a desired back-pressure in the die (die pressure) is used as input.
  • PVB sheeting having washboard or herringbone pattern was prepared on conventional extrusion equipment by varying the condition of die pressure. The same equipment was used for all of the examples. The conditions and results are given in the Table below.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Joining Of Glass To Other Materials (AREA)

Abstract

De-airing of PVB/glass laminates can be improved, while haze in the pre-press is minimized and sleep time reduced as a result using a PVB sheet having a roughened surface with directionality. A roughened surface with a washboard pattern that is useful in this regard can be obtained by varying certain conditions of a melt-fracture extrusion process.

Description

CROSS REFERENCE TO RELATED APPLICATION
This application is a continuation of pending U.S. application Ser. No. 11/335,959 filed Jan. 20, 2006, which is a continuation in part of U.S. application Ser. No. 10/204,128 filed Mar. 29, 2001, now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to glass laminates. The present invention particularly relates to laminates of glass and polyvinylbutyral, and a process of preparing same.
2. Description of Related Art
Glass laminates that include plasticized polyvinyl butyral (PVB) interlayers can be used in various applications, including use in automotive safety glass applications such as windshields and side glass; in architectural applications such as windows, doors and/or building panels; and in various other applications such as in display cases, as shelving, and the like.
Glass/PVB laminates can be prepared by conventional methods. Typically, a laminate can be prepared by first positioning a sheet of PVB between two pieces of glass to obtain an assembly, and trimming the excess PVB interlayer. A “pre-press” is obtained from the assembly by removing air trapped between the glass and the interlayer, and then sealing the edges. A conventional method for edge sealing requires placing the assembly inside of a rubber bag and removing the air from the bag by applying vacuum. The rubber bag and contents can then be passed through a furnace wherein the temperature is increased to about 135° C. in order to obtain the pre-press. A pre-press so obtained can be heated in an autoclave wherein heat and pressure are applied, residual air is dissolved in the PVB interlayer, and bonding occurs between the interlayer and the surface being laminated.
An interlayer having a smooth surface can present problems during the assembly and de-airing steps of a lamination process if a vacuum bag system is used to make the pre-press. In the assembly step, the smooth pattern allows the interlayer to tack too easily to the glass, making placement of the interlayer difficult. In the de-airing step, a smooth pattern can lead to a laminate having trapped air, and flaws in the laminate can result therefrom. It is known that interlayers having a rough surface can facilitate de-airing. Rough surface patterns can be generated by conventional methods, including use of an embossing tool to impart a reproducible pattern on the surface of the interlayer material. It is also conventional to generate a randomly irregular surface pattern by a melt-fracture process, which can provide channels by which air can escape during the lamination process.
In a typical windshield laminating process, the PVB interlayer is first subjected to a shaping step wherein the PVB interlayer is differentially stretched such that the shaped interlayer better conforms to the curvature of the vehicle for which the windshield is designed. In the shaping step, the PVB roll is unwound, and the interlayer is heated to approximately 100° C. and then passed over one or more cones which are smooth, and then chilled to approximately 10° C. for storage, and then cut into blanks slightly larger than the size of the windshield. Stresses incurred in the shaping process are partially relaxed as the blanks are conditioned at 10° C. During the shaping step, some of the pattern roughness is pressed out temporarily, but will recover according to stress relaxation kinetics well known in the art of polymer rheology.
For interlayers with surface patterns generated in a melt-fracture process, haze in a pre-press can be a problem, especially if the interlayer material is used within twelve hours of being shaped for lamination in a vacuum bag pre-pressing system. Pre-presses with less than 15% light transmission are typically rejected. Use of an embossing tool can be effective in resolving the de-airing and pre-press clarity concerns, but is more costly and more work intensive than use of a melt fracture process. An embossing process is inflexible relative to the melt fracture process, with respect to producing different patterns on the same equipment.
While use of rough patterns obtained by a melt-fracture process could improve the effectiveness of de-airing by vacuum, rough patterns generated by melt fracture require more energy to melt down in the heating step. This could render the pre-press hazier than if it had been made from a smoother interlayer. In a conventional process for making flat laminates, a glass/PVB/glass assembly is typically heated to the point where the PVB attains a temperature of abut 50-90° C. At this temperature, the entire assembly is passed through a set of nip rolls, and the nip rolls exert pressure that squeezes out the interstitial air and also seals the edges of the pre-press. Pre-presses that use conventional PVB with a roughened surface obtained by a melt fracture process tend to be hazy if Rz is above 30 micrometers.
It is desirable to obtain an interlayer material with a surface rough enough to minimize haze in a pre-press, yet maintain a desirable balance of physical properties of the interlayer, without requiring the capital investment, loss of yield, loss of flexibility, or possible contamination that can result from use of an embossing tool. Therefore it can be desirable to obtain such a rough surface without use of an embossing tool.
SUMMARY OF THE INVENTION
In one aspect, the present invention is a plasticized polyvinyl butyral sheet having a directional surface pattern created using a melt fracture process during extrusion of the sheet.
In another aspect, the present invention is a plasticized polyvinyl butyral sheet having a washboard surface pattern created using a melt fracture process during extrusion of the sheet.
In another aspect, the present invention is a plasticized polyvinyl butyral sheet having a herringbone surface pattern created using a melt fracture process during extrusion of the sheet.
In another aspect, the present invention is a process for creating a directional pattern on a surface of a plasticized polyvinyl butyral sheet using a melt fracture process during extrusion of the sheet.
In still another aspect, the present invention is a laminate comprising a plasticized polyvinyl butyral interlayer, wherein the interlayer is obtained from a polyvinyl butyral sheet having a directional surface pattern created using a melt fracture process during extrusion of the sheet.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a grey scale image of a portion of the upper surface of a polyvinyl butyral sheet having a herringbone pattern.
FIG. 2 is a grey scale image of a portion of the upper surface of a polyvinyl butyral sheet having a washboard pattern.
 DETAILED DESCRIPTION
In one embodiment, the present invention is a plasticized polyvinyl butyral (PVB) sheet having a roughened surface wherein the surface has directionality imparted by a melt fracture extrusion process. PVB sheeting of the present invention is plasticized. Conventional plasticizers known in the art of preparing PVB sheets can be used in the practice of the present invention. Such plasticizers include, but are not limited to: triethylene glycol-di-2-ethyl butyrate; triethylene glycol-di-2-ethyl hexanoate; and dibutyl sebacate.
The roughness of the surface of a PVB sheet of the present invention is such that haze in a glass/PVB pre-press is low even if the PVB is used within 12 hours after it is stretched. Surface roughness can be measured by conventional methods, and can be expressed by the term Rz. In a washboard PVB sheet of the present invention Rz is greater than about 30 micrometers, as determined by ISO R468. Preferably a washboard pattern of the present invention has a roughness of greater than about 35, more preferably greater than about 40 and most preferably from about 35 to about 100. In a herringbone pattern of the present invention, the Rz is less than about 35, preferably less than about 30, more preferably from about 15 to about 35, and most preferably from about 20 to about 30 micrometers. In a PVB sheet of the present invention, the rough surface has a directional pattern, and the rough directional pattern is obtained without use of an embossing tool.
In another embodiment, the present invention is a laminate comprising at least one layer of PVB and at least one layer of glass, wherein the PVB layer is obtained by an extrusion process wherein a roughened PVB surface having directionality is obtained without use of an embossing tool. The laminate is prepared according to conventional methods, wherein an assembly comprising at least one layer of PVB of the present invention is heated, and then de-aired under vacuum and at elevated temperature to form a pre-press. Alternatively, the laminate can be prepared by heating the assembly in an oven and then passing it through one or more pairs of nip rolls. The pre-press can be autoclaved according to conventional methods and conditions to yield a finished laminate article.
In still another embodiment, the present invention is a process for preparing a PVB sheet having a roughened surface having directionality imparted using a melt fracture extrusion process, without the aid of an embossing tool. Directionality, as the term is used herein, refers to the tendency of a roughened pattern of the present invention to have an ordered, repetitive pattern that gives the appearance of an embossed pattern. However, such a pattern is obtained without using an embossing tool. As such, problems associated with use of an embossing tool are eliminated. Problems associated with use of an embossing tool include, for example, surface defects and material loss caused by adhesion of the sheet material to the tool. A directional surface pattern of the present invention provides ordered channels that are formed by a continuous alignment of the troughs of roughened surface to provide substantially uninterrupted channels for airflow. Uninterrupted channels in a surface pattern can provide the benefit of more efficient “de-airing” in a lamination process than a surface pattern having a random array of peaks and valleys. An extruded sheet of the present invention, viewed on a 3-dimensional axis wherein the height and depth of the surface pattern is shown on the y-axis, the sheet length as it is extruded from the extruder is shown on the x-axis, and the depth of the sheet in the cross-web direction is represented on the z-axis, has channels that run in the cross-web direction and that are substantially uninterrupted by the random occurrence of a raised portion of the surface blocking the channel. The present invention provides a process for obtaining a non-random pattern having substantially uninterrupted channels in the cross-web direction without use of an embossing tool.
The process comprises varying certain conditions and parameters in the extrusion process of PVB sheeting material. To prepare conventional PVB sheeting material, typically parameters can be varied to control surface pattern. Some parameters that can be varied are die body temperature and die gap, sheet caliper, lip stream pressure, lip gap, air gap, content of plasticizer, temperature of polymer, throughput of molten polymer per unit die width, and temperature of quench water. Other parameters can be varied as well. The directional patterns of the present invention can be obtained in the process of the present invention by varying the die pressure.
Under certain die pressure operating conditions, a washboard pattern is one type of directional pattern that can be obtained on the PVB surface. A herringbone pattern is a second type of directional surface pattern that can be obtained in the process of the present invention by varying process conditions. The herringbone and washboard patterns are shown in FIG. 1 and FIG. 2, respectively. By “washboard pattern” it is meant a regular pattern having substantially uninterrupted channels wherein the troughs, or surface depressions, of an extruded sheet are aligned in the cross-web direction to form substantially straight lines. The lines can run parallel to the front edge of the extruded sheet, or can be at an angle of from about 1° to about 45°. For example, a washboard pattern can be obtained by operating at a die pressure of greater than 58 kg/cm2 (5.69 MPa). As shown in FIG. 2, a washboard pattern or surface, as the term is used herein, describes a surface having alternately high (1) and low (2) areas of elevation that form ridges (3), similar to the surface of a washboard. The ridges on a PVB surface of the present invention can be nearly parallel to the cross-web direction of the sheeting as it is extruded, the cross-web direction being the direction perpendicular to that of the extrusion. Under certain other conditions of die pressure, a herringbone pattern can be obtained on the PVB surface. By “herringbone pattern” it is meant a regular pattern having substantially uninterrupted channels wherein the troughs, or surface depressions, of an extruded sheet are aligned in the cross-web direction to form channels that appear to regularly change direction up and down in an alternating pattern, passing through a mid-line, and creating the appearance of “zig-zag” channels. For example, a herringbone pattern can be obtained by varying die pressure such that the pressure is below 37 kg/cm2 (3.63 MPa). Other patterns can be obtained by varying process conditions, but the directional patterns of the present invention are controlled primarily by the die pressure.
Throughput (rate of polymer through the die) can be in the range of from about 600 to about 1000 kg per hr per meter, depending on the equipment being used.
EXAMPLES
The Examples and comparative examples herein are included for illustrative purposes only, and are not intended to limit the scope of the present invention.
In Examples 1-25, 100 parts of dry PVB flake of nominally 18-23% by weight of un-butyralated vinyl alcohol groups were mixed with 35-40 parts of tetraethylene glycol di-n-heptanoate plasticizer and one or more light stabilizers marketed under the tradename “Tinuvin” by Ciba-Geigy Co. and an antioxidant which were pre-mixed in the plasticizer continuously in a twin-screw extruder. The melt was forced through a slot die and formed a sheeting of 0.76 mm nominal thickness. In addition, agents for modifying surface energy of the bulk interlayer and usual adjuvants such as antioxidants, colorants and ultraviolet absorbers which do not adversely affect the functioning of the surface energy modifying agent and adhesion control agent can be included in the PVB composition. The melt at the die is at approximately 200-220° C. The lips of the die are heated by injecting pressurized steam into cavities therein. The lip temperature is controlled by the pressure of the steam injected. One of the die lips is adjustable so that as it opens, the back-pressure in the die is decreased and vice versa. The position of this lip is computer-controlled, and a desired back-pressure in the die (die pressure) is used as input.
PVB sheeting having washboard or herringbone pattern was prepared on conventional extrusion equipment by varying the condition of die pressure. The same equipment was used for all of the examples. The conditions and results are given in the Table below.
TABLE
Washboard (W) or Lip Steam
Herringbone (H) or Die Pressure Pressure Rz (average)
Ex. No. Random (R) (kg/cm2) (kg/cm2) (micrometers)
1 W 58.8 6.5 62.8
2 H 35.5 6.5 24.4
3 H 35.5 6.5 24.7
4 H 33.5 6.5 29.0
5 H 31.5 6.5 27.2
6 H 29.2 6.5 24.4
7 H 33.6 6.5 28.1
8 H 33.4 6.5 27.6
9 H 33.8 15 26.7
10 H 34.1 15 26.6
11 H 36.0 15 24.3
12 R 62.9 15 47.9
13 R 63.0 10 75.2
14 W 62.8 6.5 80.0
15 W 58.2 6.5 54.5
16 W 58.4 6.5 63.9
17 W 59.3 6.5 60.5
18 W 58.5 6.5 65.1
19 W 58.7 6.5 60.2
20 W 58.6 6.5 65.1
21 W 58.7 6.5 66.5
22 W 60.3 6.5 73.3
23 W 60.0 6.5 70.9
24 W 58.4 6.5 59.8
25 W 60.1 6.5 81.9
Comparative Example 26
Twenty full size windshields were prepared using a PVB interlayer commercially available from DuPont under the trade name Butacite® BE-1120 with a random surface pattern generated by melt fracture. The die pressure used was 62.9 kg/cm2 (61.7 MPa), lip steam pressure was 15 kg/cm2 (14.7 MPa). The roughness in terms of Rz was 47.9 micrometers, but there was no directionality. The interlayer was shaped using typical shaping equipment, and the shaped interlayer was allowed to recover at about 15° C. for 4 hours. The pre-presses were prepared using a commercial vacuum-bag system with approximately 5 minutes of vacuum at ambient temperature, and 10 minutes inside an oven in which the PVB temperature gradually rose to about 100° C. at the end of that period. Ten of the pre-presses were very hazy, and were judged to be unusable (50% yield).
Comparative Example 27
Another twenty full size windshields were made of the same interlayer as in Comparative Example 26 except that the shaped interlayers had 8 hours of recovery after shaping. Five of the pre-presses were judged unusable (75% yield). This example shows that longer recovery time improves pre-press yield.
Example 28
Twenty windshields were prepared using the procedure in Comparative Example 26, except that the interlayer had washboard pattern, and Rz was 62.8 micrometer. It was made with die pressure of 58.8 kg/cm2 (57.7 MPa) and lip steam pressure of 6.5 kg/cm2 (6.4 MPa). The interlayer had 4 hours of recovery time after shaping before it was assembled. One of the twenty pre-presses was judged unusable (95% yield). The pre-press yield was much higher than that in Comparative Example 26 although the sheeting was rougher, leading one skilled in the art to suspect that the pre-press would be hazier.
Example 29
Twenty windshields were prepared as in Example 28, except that the interlayer had 8 hours of recovery time after shaping before it was assembled. None of the twenty windshields was judged unusable (100% yield).

Claims (6)

1. A process for creating a directional pattern on a surface of a polyvinyl butyral sheet comprising the step of extruding molten polyvinyl butyral using a melt fracture extrusion process, wherein the pattern can be controlled by varying extruder die pressure and wherein an embossing tool is not used, characterized in that the directional pattern is a herringbone pattern that is created using a die pressure of from 29.2 to 36.0 kg/cm2.
2. A process of claim 1 additionally characterized in that extruder lip steam pressure is 15 kg/cm2 or less.
3. A process of claim 2 wherein the lip steam pressure is 10 kg/cm2 or less.
4. A process for producing a laminate comprising the steps of
A. forming a polyvinyl butyral sheet having a directional surface pattern by extruding molten polyvinyl butyral using a melt fracture extrusion process, wherein the pattern can be varied by varying extruder die pressure and wherein an embossing tool is not used, characterized in that the directional pattern is a herringbone pattern created using a die pressure of from 29.2 to 36.0 kq/cm2; and
B. forming a layered assembly comprising said polyvinyl butyral sheet by contacting said polyvinyl butyral sheet with at least one layer of glass;
C. forming a pre-press by heating and de-airing said layered assembly under vacuum; and
D. heating said pre-press in an autoclave while applying heat and pressure to bond said polyvinyl butyral sheet and said at least one glass layer, thereby forming a laminate.
5. A process of claim 4 wherein the layered assembly is heated to a temperature of at least 100° C. during formation of the pre-press.
6. A process of claim 4 wherein the polyvinyl butyral layer is differentially stretched during formation of the pre-press.
US12/507,273 2002-08-14 2009-07-22 Glass/polyvinylbutyral laminates having directional surface patterns and a process for preparing same Expired - Fee Related US8025826B2 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
US12/507,273 US8025826B2 (en) 2002-08-14 2009-07-22 Glass/polyvinylbutyral laminates having directional surface patterns and a process for preparing same

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
US10/204,128 US20030012964A1 (en) 2000-03-29 2001-03-29 Glass/polyvinylbutyral laminates having directional surface patterns and a process for preparing same
US11/335,959 US20060263608A1 (en) 2002-08-14 2006-01-20 Glass/polyvinylbutyral laminates having directional surface patterns and a process for preparing same
US12/507,273 US8025826B2 (en) 2002-08-14 2009-07-22 Glass/polyvinylbutyral laminates having directional surface patterns and a process for preparing same

Related Parent Applications (1)

Application Number Title Priority Date Filing Date
US11/335,959 Continuation US20060263608A1 (en) 2002-08-14 2006-01-20 Glass/polyvinylbutyral laminates having directional surface patterns and a process for preparing same

Publications (2)

Publication Number Publication Date
US20090277573A1 US20090277573A1 (en) 2009-11-12
US8025826B2 true US8025826B2 (en) 2011-09-27

Family

ID=46323663

Family Applications (2)

Application Number Title Priority Date Filing Date
US11/335,959 Abandoned US20060263608A1 (en) 2002-08-14 2006-01-20 Glass/polyvinylbutyral laminates having directional surface patterns and a process for preparing same
US12/507,273 Expired - Fee Related US8025826B2 (en) 2002-08-14 2009-07-22 Glass/polyvinylbutyral laminates having directional surface patterns and a process for preparing same

Family Applications Before (1)

Application Number Title Priority Date Filing Date
US11/335,959 Abandoned US20060263608A1 (en) 2002-08-14 2006-01-20 Glass/polyvinylbutyral laminates having directional surface patterns and a process for preparing same

Country Status (1)

Country Link
US (2) US20060263608A1 (en)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10155877B2 (en) 2013-10-30 2018-12-18 C-Bond Systems, Llc Materials, treatment compositions, and material laminates, with carbon nanotubes

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US20080254302A1 (en) 2007-04-13 2008-10-16 David Paul Bourcier Multiple layer polymer interlayers having a melt fractured surface
US20080268204A1 (en) * 2007-04-29 2008-10-30 David Paul Bourcier Multiple layer polymer interlayers having an embossed surface
US8349458B2 (en) * 2007-11-06 2013-01-08 Solutia Inc. Interlayers comprising glycerol based plasticizer
JP4852070B2 (en) * 2008-06-16 2012-01-11 三菱電機株式会社 Plant monitoring and control system
WO2012133668A1 (en) * 2011-03-29 2012-10-04 株式会社クラレ Poly(vinyl acetal) resin film and multilayer structure using same
JP6568356B2 (en) 2013-08-01 2019-08-28 積水化学工業株式会社 Method for manufacturing vehicle windshield
EP3006202A1 (en) * 2014-10-08 2016-04-13 Kuraray Europe GmbH Multilayer films of plasticizer-containing polyvinyl acetal with photochromic properties
WO2017022686A1 (en) * 2015-07-31 2017-02-09 積水化学工業株式会社 Intermediate film for laminated glass, method for producing intermediate film for laminated glass, and laminated glass
EP3440117B1 (en) 2016-04-08 2021-09-29 Kuraray Europe GmbH Polyvinyl acetal with reduced flowability
WO2017174682A1 (en) * 2016-04-08 2017-10-12 Kuraray Europe Gmbh Multilayer film comprising layer of plasticized polyvinyl acetal with reduced flowability
EP3569408A1 (en) * 2018-05-15 2019-11-20 Kuraray Europe GmbH Interlayer films having asymmetric surface roughness

Citations (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2489951A (en) 1946-06-22 1949-11-29 Monsanto Chemicals Extrusion apparatus
US3994654A (en) * 1975-01-02 1976-11-30 Monsanto Company Die for extruding thermoplastic sheets
US4452840A (en) 1981-03-12 1984-06-05 Mitsubishi Monsanto Chemical Company Plastic interlayer for lamination with heights of 10 to 500 microns
EP0211819A1 (en) 1985-07-02 1987-02-25 Monsanto Company Polyvinyl butyral sheet roughness control
EP0215976A1 (en) 1984-03-30 1987-04-01 Sekisui Kagaku Kogyo Kabushiki Kaisha Interlayer for laminated glass
US4925725A (en) 1984-03-30 1990-05-15 Sekisui Kagaku Kogyo Kabushiki Kaisha Interlayer for laminated glass
EP0390578A2 (en) 1989-03-31 1990-10-03 Sekisui Kagaku Kogyo Kabushiki Kaisha Method of manufacturing thermoplastic resin sheets
US5425977A (en) 1993-08-16 1995-06-20 Monsanto Company Rough-surfaced interlayer
US5455103A (en) 1994-01-24 1995-10-03 Monsanto Company Rough-surfaced interlayer
US5626809A (en) 1994-05-30 1997-05-06 Tale Consultants, T.D. Method for making a film of polyvinyl butyral used for making laminated glass
US6048939A (en) * 1997-01-09 2000-04-11 Dupont Dow Elastomers, L.L.C. Process aid for melt processible polymers
US6077374A (en) 1993-08-16 2000-06-20 Monsanto Method of preparing prelaminate using rough-surfaced interlayer
US6093471A (en) * 1999-02-08 2000-07-25 Solutia Inc. Polyvinyl butyral sheet
WO2001072510A2 (en) 2000-03-29 2001-10-04 E.I. Dupont De Nemours And Company Glass/polyvinylbutyral laminates having directional surface patterns and a process for preparing same
JP2002261620A (en) 2000-12-28 2002-09-13 Victor Co Of Japan Ltd Modulation method, modulation device, demodulation device, demodulation method and record medium
JP2002301417A (en) 2001-04-09 2002-10-15 Konica Corp Coating device and method
JP2009508078A (en) 2005-09-08 2009-02-26 デーウー・エレクトロニクス・コーポレイション Refrigerated storage using thermoelectric elements
JP2009301417A (en) 2008-06-16 2009-12-24 Mitsubishi Electric Corp Plant monitoring control system

Patent Citations (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2489951A (en) 1946-06-22 1949-11-29 Monsanto Chemicals Extrusion apparatus
US3994654A (en) * 1975-01-02 1976-11-30 Monsanto Company Die for extruding thermoplastic sheets
US4452840A (en) 1981-03-12 1984-06-05 Mitsubishi Monsanto Chemical Company Plastic interlayer for lamination with heights of 10 to 500 microns
EP0215976A1 (en) 1984-03-30 1987-04-01 Sekisui Kagaku Kogyo Kabushiki Kaisha Interlayer for laminated glass
US4925725A (en) 1984-03-30 1990-05-15 Sekisui Kagaku Kogyo Kabushiki Kaisha Interlayer for laminated glass
EP0211819A1 (en) 1985-07-02 1987-02-25 Monsanto Company Polyvinyl butyral sheet roughness control
US4654179A (en) 1985-07-02 1987-03-31 Monsanto Company Polyvinyl butyral sheet roughness control
EP0390578A2 (en) 1989-03-31 1990-10-03 Sekisui Kagaku Kogyo Kabushiki Kaisha Method of manufacturing thermoplastic resin sheets
US5151234A (en) 1989-03-31 1992-09-29 Sekisui Kagaku Kogyo Kabushiki Kaisha Method for the manufacture of thermoplastic resin sheets
US6077374A (en) 1993-08-16 2000-06-20 Monsanto Method of preparing prelaminate using rough-surfaced interlayer
US5425977A (en) 1993-08-16 1995-06-20 Monsanto Company Rough-surfaced interlayer
US5455103A (en) 1994-01-24 1995-10-03 Monsanto Company Rough-surfaced interlayer
US5626809A (en) 1994-05-30 1997-05-06 Tale Consultants, T.D. Method for making a film of polyvinyl butyral used for making laminated glass
US6048939A (en) * 1997-01-09 2000-04-11 Dupont Dow Elastomers, L.L.C. Process aid for melt processible polymers
US6093471A (en) * 1999-02-08 2000-07-25 Solutia Inc. Polyvinyl butyral sheet
WO2001072510A2 (en) 2000-03-29 2001-10-04 E.I. Dupont De Nemours And Company Glass/polyvinylbutyral laminates having directional surface patterns and a process for preparing same
EP1268196A2 (en) 2000-03-29 2003-01-02 E.I. Dupont De Nemours And Company Glass/polyvinylbutyral laminates having directional surface patterns and a process for preparing same
US20030012964A1 (en) 2000-03-29 2003-01-16 Choi Chul Won Glass/polyvinylbutyral laminates having directional surface patterns and a process for preparing same
JP2002261620A (en) 2000-12-28 2002-09-13 Victor Co Of Japan Ltd Modulation method, modulation device, demodulation device, demodulation method and record medium
JP2002301417A (en) 2001-04-09 2002-10-15 Konica Corp Coating device and method
JP2009508078A (en) 2005-09-08 2009-02-26 デーウー・エレクトロニクス・コーポレイション Refrigerated storage using thermoelectric elements
JP2009301417A (en) 2008-06-16 2009-12-24 Mitsubishi Electric Corp Plant monitoring control system

Non-Patent Citations (13)

* Cited by examiner, † Cited by third party
Title
Figure submitted in Opposition as E3.
Figure submitted in Opposition as E4.
Figure submitted in Opposition as E5.
File History: EP 1 268 196.
HT Troplast AG invoice cited in Opposition as E6.
HT Troplast AG invoice cited in Opposition as E7.
International Preliminary Examination Report from PCT Counterpart PCT/US01/10023.
International Search Report from PCT Counterpart PCT/US01/10023.
Michaeli, Extrusionwerkzeuge fur Kunststoffe usw ("Extrusion tools for plastics etc..").
Opposition filed by Kuraray Specialities Europe GmbH against European counterpart EP 1 268 196 B1.
Response dated Jul. 24, 2006, to Oppostlon filed by Kuraray Specialities Europe GmbH against European counterpart EP 1 268 196 B1, including amended claims.
Test results submitted in Opposition as E8.
Written Opinion from PCT Counterpart PCT/US01/10023.

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10155877B2 (en) 2013-10-30 2018-12-18 C-Bond Systems, Llc Materials, treatment compositions, and material laminates, with carbon nanotubes

Also Published As

Publication number Publication date
US20060263608A1 (en) 2006-11-23
US20090277573A1 (en) 2009-11-12

Similar Documents

Publication Publication Date Title
US8025826B2 (en) Glass/polyvinylbutyral laminates having directional surface patterns and a process for preparing same
CA2399724C (en) Glass/polyvinylbutyral laminates having directional surface patterns and a process for preparing same
EP0714350B1 (en) Rough-surfaced interlayer
EP2646248B1 (en) Systems and method for direct embossment of a polymer melt sheet
AU2001247870A1 (en) Glass/polyvinylbutyral laminates having directional surface patterns and a process for preparing same
KR101558835B1 (en) Multiple layer polymer interlayers having a melt fractured surface
EP1458564B1 (en) Glass lamination process and apparatus
CN103921509B (en) There is the multiple layer polymer intermediate layer of embossed surface
US7117914B2 (en) Non-autoclave laminated glass
EP3186059B1 (en) Process for production of embossed films based on plasticized polyvinyl acetal
CN107619202B (en) Interlayer film for laminated glass and laminated glass comprising same
JP2001048599A (en) Interlayer for laminated glass
JP2003212614A (en) Interlayer for laminated glass
TWI488734B (en) Interlayer for laminated glass and laminated glass containing the same and the method of using the interlayer to improve the properties of the laminated glass
JP2000319045A (en) Interlayer for laminated glass and laminated glass
JPH06198809A (en) Intermediate film for safety glass
US20240375378A1 (en) Polymer interlayers with low mottle and reduced iceflower defects
US11597186B2 (en) Laminating film and light-transmitting laminate including same
JPH08143346A (en) Method for producing interlayer film for laminated glass
JPH05294680A (en) Intermediate film for laminated glass
JP2000256044A (en) Method for producing interlayer film for laminated glass
JPH09241044A (en) Interlayer for laminated glass

Legal Events

Date Code Title Description
ZAAA Notice of allowance and fees due

Free format text: ORIGINAL CODE: NOA

ZAAB Notice of allowance mailed

Free format text: ORIGINAL CODE: MN/=.

STCF Information on status: patent grant

Free format text: PATENTED CASE

AS Assignment

Owner name: KURARAY AMERICA INC., TEXAS

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:E. I. DU PONT DE NEMOURS AND COMPANY;REEL/FRAME:033420/0538

Effective date: 20140723

FPAY Fee payment

Year of fee payment: 4

MAFP Maintenance fee payment

Free format text: PAYMENT OF MAINTENANCE FEE, 8TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: M1552); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

Year of fee payment: 8

FEPP Fee payment procedure

Free format text: MAINTENANCE FEE REMINDER MAILED (ORIGINAL EVENT CODE: REM.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

LAPS Lapse for failure to pay maintenance fees

Free format text: PATENT EXPIRED FOR FAILURE TO PAY MAINTENANCE FEES (ORIGINAL EVENT CODE: EXP.); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362

FP Lapsed due to failure to pay maintenance fee

Effective date: 20230927